Systems for promoting endothermic conversions with oxygen transfer agents

ABSTRACT

A system for promoting endothermic conversions includes a first and second portion, a first and second supply, a first outlet, and a heat exchanger. The first portion defines a first inner volume containing an oxygen transfer agent. The first supply contains a reducing agent and is fluidly connected to the first inner volume. The first outlet conveys one or more of carbon dioxide, water, and an unsaturated hydrocarbon from the first inner volume. The second portion and the heat exchanger positioned within the second portion define a second inner volume containing reduced oxygen transfer agent. The second supply contains an oxidizing agent fluidly connected to the second inner volume. The heat exchanger also defines a third inner volume segregated from the second inner volume, and the heat exchanger is configured to transfer heat resulting from the oxidation of the reduced oxygen transfer agent to the third inner volume.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. application Ser. No.15/738,212, filed Dec. 20, 2017, which is a U.S. national phaseapplication of PCT International Application PCT/US2016/038512, filedJun. 21, 2016, and claims the benefit of priority to U.S. ProvisionalApplication Nos. 62/183,048, entitled COUPLING OF EXOTHERMIC ANDENDOTHERMIC REACTIONS IN HYDROCARBON DEHYDROGENATION VIA CHEMICALLOOPING, and 62/184,620, entitled HEAT TRANSFER AGENTS FOR OXIDATIVEDEHYDROGENATION OF HYDROCARBONS, filed on Jun. 22, 2015 and Jun. 25,2015, respectively, the contents of which are incorporated herein byreference in their entireties for all purposes.

FIELD OF THE INVENTION

The invention relates to reactor systems and processes that utilizeoxygen transfer agents for the oxidative dehydrogenation (ODH) ofhydrocarbons, specifically oxygen transfer agents and blends thereofhaving a high thermal effusivity.

BACKGROUND OF THE INVENTION

Ethylene and propylene are important building blocks for thepetrochemical industry. These olefins are used in the manufacturing ofpolymers such as polyethylene, polypropylene, polystyrene and many morechemicals of commercial interest. Over 90% of the global olefinproduction comes from the high temperature steam cracking of naphtha orethane and propane. The steam cracking process, which utilizes furnaces,is highly energy intensive, and 1.5 to 2 tons of carbon dioxide isproduced for every ton of olefin product.

Natural gas production from shale deposits has dramatically increasedsupply in recent years. As a result of the continued global demand forolefins and the potential for a new growing supply of ethane and propaneavailable in natural gas liquids from shale deposits, a significantamount of interest and investment is currently centered around expandingthe capacity of ethylene and propylene derived from these new sources.Numerous olefin grass root and expansion projects are either undercontract or in the planning stages to take advantage of the relative lowcost liquids from wet shale gas. However, there are many environmentaland cost challenges to bringing on this level of new capacity.

Olefin production is the largest emitter of CO₂ and NOR in the organicchemical industry. With worldwide ethylene production at ˜150 MT/yr, theindustry emits 150-300 MT/yr of CO₂ and roughly 1.4 MT/yr of NOR.Projects located in severe EPA non-attainment zones are challenged bythe increased cost of NOx control. The total greenhouse gas (GHG)emission profile, reported in CO₂ equivalents, is another critical partof the permitting for all production expansions.

The industry continues to push for production technology that: (1)generates higher overall yield of ethylene and propylene; (2) increasesthe run length between furnace turnarounds (e.g. inspections, repairs,improvements, etc.); (3) lowers steam and energy utilization; and (4)lowers all GHGs including carbon dioxide and NOR. ODH of ethane andpropane offers a potential solution for these needs.

The ODH of ethane and propane to olefins offers a production route thatcan significantly reduce CO₂ emissions and virtually eliminate NORemissions from world scale plants. ODH is a selective catalytic processthat produces primarily ethylene and water as products, and is therebyan exothermic reaction (reaction 1).

CH₃CH₃+½ O₂→CH₂CH₂+H₂O ΔH_(o)=−105 kJ/mol   (1)

The per pass yield of the ODH reaction is not limited by thermodynamicequilibrium, as it is in pyrolysis, (reaction 2).

CH₃CH₃+Heat⇄CH₂CH₂+H₂ ΔH_(o)=+137 kJ/mol   (2)

ODH provides an opportunity to achieve some of the objectives to improvethe efficiency of olefin production. Therefore, there is a need forimproved reactors and processes for facilitating efficient ODHconversions.

SUMMARY OF THE INVENTION

It is a first aspect of the present invention to provide a system forpromoting endothermic conversions. The system may comprise a first andsecond portion, a first and second supply, and a heat exchangerpositioned within the second portion. The first portion may define afirst inner volume at least partially filled with an oxygen transferagent. The first supply may contain one or more of hydrogen and asaturated hydrocarbon fluidly connected to a first inlet of the firstinner volume. The second supply may contain an oxidizing agent fluidlyconnected to a second inlet to the second inner volume. The system mayfurther comprise a first outlet for conveying one or more of carbondioxide, water, and an unsaturated hydrocarbon from the first innervolume. The second portion and the heat exchanger may define a secondinner volume at least partially filled with reduced oxygen transferagent The heat exchanger may also define a third inner volume segregatedfrom the second inner volume and be configured to transfer heatresulting from the oxidation of the reduced oxygen transfer agent in thesecond inner volume to the third inner volume.

It is another aspect of the present invention to provide a method ofpromoting endothermic conversions. The method may comprise contacting asaturated hydrocarbon with an oxygen transfer agent resulting in areduced oxygen transfer agent and an unsaturated hydrocarbon, contactingthe reduced oxygen transfer agent with an oxidizing agent resulting inan exothermic reaction, and transferring heat from the exothermicreaction to a heat exchanger to promote an endothermic conversion withinthe heat exchanger. The heat exchanger may be positioned within a vesseland the vessel and the heat exchanger may define a first inner volume atleast partially filled with the reduced oxygen transfer agent, and theheat exchanger may define a second inner volume segregated from thefirst inner volume.

BRIEF DESCRIPTION OF THE FIGURES

In order that the invention may be more fully understood, the followingfigures are provided by way of illustration, in which:

FIG. 1 is a schematic of an ODH Chemical Looping Mechanism utilizing anoxygen transfer agent;

FIG. 2A is a schematic of a circulating bed reactor system according toone embodiment of the present invention; and

FIG. 2B is a schematic of a dual fixed bed reactor system according toone embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Although the invention is illustrated and described herein withreference to specific embodiments, the invention is not intended to belimited to the details shown. Rather, various modifications may be madein the details within the scope and range of equivalents of the claimsand without departing from the invention.

It is a first aspect of the present invention to provide a system thatutilizes the exothermic heat of reaction, enthalpy, from an ODH processin an integrated process in order to maximize the overall energyefficiency of the process. As examples, the heat of reaction may be usedto heat up feeds to reaction temperature and/or generate steam fordriving compressors or turbines for electricity generation. Anotheraspect of the present invention provides a system wherein the exothermicheat of reaction from the oxidation of a reduced oxygen transfer agentmay be used to promote an endothermic reaction. By efficiently utilizingthe exothermic heat of reaction from the oxidation of a reduced oxygentransfer agent, the release of GHG that would typically occur from theburning of fossil fuels for promoting endothermic reactions may beavoided.

The embodiments of the present invention eliminate or reduce theemission of carbon dioxide and nitrogen oxide by-products by relying on“flameless” combustion or oxidation using the unique properties of manysolid oxide transfer agents (M) shown in equations (3) and (4),

M+½ O₂→MO   (3)

MO+Reductant→M+Products+H₂O   (4).

In equation (4), the reductant is converted to products and water. Inreactors and processes according to the present invention, it ispreferred that the heat released, enthalpy of reaction (3), is largerthan the heat required for reaction (4). It is further preferred thatthe solid oxide transfer agents used for flameless combustion in thevarious embodiments of the present invention have high heats ofreaction, are able to transfer a high percent of the oxide weight tooxygen upon reduction, and have high thermal and physical stability topreserve the activity of the metal/metal oxide and reduce particleattrition in moving or fluid bed applications. Examples of solid oxidetransfer agents that may be used in the reactors and processes accordingto the various embodiments of the present invention are found in Table1.

TABLE 1 Oxide Reduced Wt. % releasable ΔHo for reaction (3) TransferAgent form oxygen kJ/mol Fe₂O₃ Fe 30.1 −1,652 MnO₂ MnO 18.40 −269.6 CuOCu 20.1 −314.6

The systems and processes according to the embodiments of the presentinvention may be configured to use the exothermic heat of reaction froman ODH process to promote an endothermic chemical conversion. The solidoxide transfer agents of the systems and processes of the presentinvention preferably have high transferable oxygen content andsignificant heat release when they are oxidized from their reduced form.To facilitate heat release, the solids should have high heat capacityand the ability to transfer their heat energy to the environment at highrates, i.e., a high Thermal Effusivity. Thermal Effusivity (“e”) is theproduct of a material's volumetric heat capacity (“Cp”) and its thermalconductivity (“k”), taken to the 0.5 power, equation (5).

e=(kρC _(p))^(0.5)   (5)

Thus, Thermal Effusivity of a material is a measure of its ability tochange the thermal energy in its environment. An illustrative list ofthe thermal effusivity of a few materials is provided in Table 2.

TABLE 2 Thermal Effusivity Examples Specfic Material Heat ThermalThermal Density Capacity Conductivity Effusivity Material Kg/m³ J/Kg-KW/m-K W.s^(0.5)/m²-K magnesium oxide 3580 921 61.923 14285 (mgo)(polyxtal, 100 d) manganese oxide 4200 628 4.184 3321 (mn3o4) (87 pcdense) iron oxide (fe2o3) 5240 628 12.552 6425 (hematite) copper oxide(cuo) 6500 536 17.991 7914 (tenorite) aluminum oxide 3980 778 38.49310919 (al2o3) (polyxtal 100 d) aluminum 2698 921 225.94 23688 silicaglass, fused or 2200 745 1.381 1504 vitrous silicon carbide (sic) (kt3100 678 179.91 19443 grade) copper 8940 385 397.48 36983 tantalumcarbide + wc 15300 209 66.944 14638 cermet k601 tungsten carbide 14100209 91.63 16440 cermet k94 and k1 zinc-aluminum alloy 6600 418 112.9717662 astm 23 zinc-aluminum-copper 6700 418 108.78 17463 alloy astm 25

It is preferred that the solid oxygen transfer agents used in thesystems and processes of the present invention have thermal effusivitiesof at least 3,500 and, more preferably, at least 10,000 W·s^(0.5)/m²−K.In another embodiment, oxygen transfer agents incorporated in thesystems and processes of the present invention may comprise one or moreoxygen transfer agents having a high thermal effusivity and an oxygentransfer agent that is highly active and selective for ODH. For examplein one embodiment, a system may include a blend of oxygen transferagents comprising manganese, alkali metals, and tungsten carbide.

Oxygen transfer agents that are highly active and selective for ODH mayinclude materials used for the ODH of hydrocarbons following thegeneralized formula of Equation 6:

zC_(n)H_(2n+2−2β)+(z−1+δ)“O”→C_((z×n))H_(2(2×n)+2−2β−2δ)+(z−1+δ) H₂O  (6)

where z=the number of reacting molecules; n=the number of atomic unitsin the reacting molecule; β=the degree of unsaturation where the valueis zero for single bonds, one for double bonds and molecular rings, andtwo for triple bonds; and δ=the change in the degree of unsaturation.The oxygen, “O” in Equation 6 may be supplied by the reduction of ametal oxide or via the catalytic use of molecular oxygen.

The oxygen transfer agents may also be useful for the case of Equation6, where the carbon number, n, is equal to one. In this case the usefulreaction promoted by these agents is called the oxidative coupling ofmethane (OCM) to higher hydrocarbons.

A few examples of the reactions described by Equation 6 that may bepromoted using an oxygen transfer agent according to the presentinvention are shown in Table 3.

TABLE 3 Number of Degree Change of Moles Starting starting Cnunsaturation unsaturation Moles of Molecule, mole- Starting in startingin of oxygen Cn Hn Product Product CnHy cules = z material molecule = βproduct = α water (O₂) Product Product Formula Name CH₄ 6 1 0 4 9 4.5 66 C₆H₆ Benzene C₃H₈ 2 3 0 1 2 1 6 12 C₆H₁₂ Hexene C₂H₆ 2 1 0 2 3 1.5 4 6C₄H₆ Butyne CH₄ 2 3 0 1 2 1 2 4 C₂H₄ Ethylene C₄H₈ 1 2 1 1 1 0.5 4 6C₄H₆ Butyne C₃H₆ 2 1 1 2 3 1.5 6 8 C₆H₈ Cyclohex adiene CH₄ 2 4 0 0 10.5 2 6 CH₃CH₃ Ethane CH₃CH₃ 1 3 0 1 1 0.5 2 4 CH₂CH₂ Ethylene

While promoting the conversion of hydrocarbons according to a reactionaccording to Equation (6), the oxygen transfer agent is reduced from anoxidized state to a less oxidized, i.e. reduced, state. In order toregenerate the agent, oxygen may be used to re-oxidize the reducedagent. This re-oxidation process may occur concurrent with the reductionof the oxygen transfer agent in the presence of one or more oxidationagent(s) such as oxygen, air, carbon dioxide, steam, NOx, and/or oxidesof sulfur. A preferred embodiment of this invention is the re-oxidationof the oxygen transfer agents in a separate step. Thisreduction/oxidation of the oxygen transfer agent with concurrentformation of useful products, which is schematically illustrated in FIG.1, is often described as a redox or chemical looping system.

There are many benefits of processing the ODH reaction in a chemicallooping mode which include:

-   -   Ability to use inexpensive air vs. expensive oxygen via air        separation equipment.    -   Heat balance and temperature control of reactor system via the        circulation of high heat capacity solids, allowing a        self-sustainable operation from an energy balance standpoint.    -   Ability to separate the oxidation of the hydrocarbon from the        re-oxidation of the oxygen transfer agent, thereby allowing for        separate reaction conditions of temperature and pressure for the        two different steps.    -   Higher selectivity and yield to the desired products of Equation        1, with minimization of unwanted products, such as carbon        oxides, than observed when the oxidation is carried out over a        catalyst in a co-feed of hydrocarbon and oxygen. The presence of        the oxygen transfer agent also drives the dehydrogenation        equilibrium towards the product side.    -   Use of highly efficient, high through-put reactor systems.    -   Near zero emission of both carbon dioxide, sulfur oxides and        nitrogen oxides.    -   Near zero coke accumulation on the oxygen transfer agent.

In a preferred embodiment of the present invention, a solid oxygentransfer agent is comprised of a mixed oxide preferably with Mixed IonicElectronic Conductivity (MIEC). MIEC materials useful in this inventionpromote Equation 6 at high rates and selectivities to the desired ODHproducts with minimal production of unwanted products such as carbonoxides or coke. The MIEC may have a strong ability to carry the reactiveoxygen moiety (“O”) into the reactor to perform a reaction according toEquation (6), and also be facile for the reaction to regain its activestate. The solid oxygen transfer may also have a high ThermalEffusivity, so that the heat generated by the material from a reactionaccording to Equation (4) may be used to drive an endothermic reactionaccording to Equation (3).

Examples of MIEC materials that may be used in the systems and processesaccording to the various embodiments of the present invention aredisclosed in International Patent Publication WO 2016/049144 A1, thecontents of which are incorporated herein by reference.

The oxygen transfer agents used in the systems and processes accordingto the various embodiments of the present invention may further includea promoter that serve to promote higher selectivity to specific desiredproducts. While not wishing to be bound to theory, it is believed thatactive oxygen is drawn to the promoter sites within the oxygen transferagent. This enables the oxygen transfer agents to act as a selectivepromoter of a reaction according to Equation (6) and as an oxygenreservoir to the selective promoting agent.

The oxygen transfer agents according to the present invention may beporous, or dense, in so much as effective mass transport of reactants ismaintained. The contact time of the feed hydrocarbons or the feedoxidant, typically air, with the oxygen transfer agent may be 0.01seconds to 60 seconds, when calculated at reaction conditions oftemperature and pressure. More typically, the contact time will be inthe range of 0.1 to 20 seconds. The reaction contact times are optimizedto produce the highest yield of the desired product of oxidation.

The conventional manufacturing process for ethylene, steam cracking,requires a high amount of heat to drive the endothermic cracking ofethane to ethylene and hydrogen, as shown in Equation 7, Table 4.

TABLE 4 Relevant Thermodynamic Values ΔH^(1,100K) ΔG^(1,100K) ReactionkJ/mol* kJ/mol*  7) CH₃CH₃ → CH₂CH₂ + H₂ 143 −4.9  8) CH₄ + 2 O₂ → CO₂ +2 H₂O −802 −800  9) CH₃CH₃ + ½ O₂ → CH₂CH₂ + H₂O −105 −192 10) CH₃CH₃ +3½ O₂ → 2 CO₂ + 3 H₂O −1429 −1485 11) 3 MnO + O₂ → Mn₃O₄ −223 −99.3 12)H₂ + ½ O₂ → H₂O −248 −187 13) Mn₃O₄ + H₂ → 3 MnO + H₂O 14) CH₃CH₃ +Mn₃O₄ → 118 −92.6 CH₂CH₂ + H₂O +MnO

In principle, oxygen may be reacted directly with ethane to produceethylene in an oxy-pyrolysis reaction (Equation (9) in Table 4).However, high yields of ethylene compete with the thermodynamically andkinetically favored product, carbon dioxide (Equation (8) in Table 4).

The selective oxidation of hydrocarbons to olefins, such as ethane toethylene, may be promoted in a chemical looping sequence, according toreactions (15) and (16) and shown in FIG. 1.

CH₃CH₃+MeOx→CH₂CH₂+MeO_(x-1)+H₂O   (15)

MeO_(x-1)+½ O₂ (air)→MeOx+heat   (16)

Systems according to various embodiments of the present invention may beconfigured as a chemical looping system comprising an oxygen transferagent having an exothermic heat of reaction when it is oxidized and anendothermic heat of reaction when it is reduced. For example referringto Table 4, manganese oxide if used as an oxygen transfer agent wouldprovide an endothermic heat of reaction when converting ethane toethylene (Equation 14); however, re-generating the manganese oxide ofoxygen would provide an exothermic heat of reaction (Equation 11).

As noted above, it is an aspect of the present invention to providesystems and processes that will improve the heat management and overallyield of an ODH reaction. It is preferred that the oxygen transferagents used in the systems and processes of the present invention arecapable of selectively promoting a reaction according to Equation (6),have an exothermic heat of oxidation, and a heat of reduction that isless exothermic than the heat of oxidation, more preferably, a heat ofreduction that is endothermic. The reactors and processes according tothe present invention may be configured as fixed or circulating bedreactors. In the case of fixed bed reactors, multiple reactors may beused such that hydrocarbon oxidation and oxygen transfer agentre-oxidation are occurring continuously as feed and air is alternatelycycled to various reactors. Circulating bed reactors in systemsaccording to the present invention may circulate solids from ahydrocarbon reactor zone to an oxygen transfer agent regeneration zone,such as a Mars-van Krevelen-like mechanism, as illustrated in FIG. 1.Such systems would require means for transferring the reduced andre-generated oxygen transfer agents between the zones, such asfluidized, ebullating, or entrained beds, as well as other means knownby those of skill in the art. The circulation of the solid oxygentransfer agent may be co-current or counter current to the gas feed tothe vessel.

A circulating bed system 3 according to an embodiment of the presentinvention is shown in FIG. 2A. A reduction zone 4 is at least partiallyfilled with an oxygen transfer agent (not shown). A reductant, such ashydrogen and/or a saturated hydrocarbon, such as ethane, is fed throughinlet 6 into the reduction zone 4 causing reduction of the oxygentransfer agents upon contacting the reductant. Products leaving outlet 7from the reduction zone 4 may include at least one of water, carbondioxide, or unsaturated hydrocarbons, such as ethylene. The solid oxygentransfer agent in reduction zone 4 preferably has a high selectivitypreference for being reduced by hydrogen, so that the reductant suppliedin inlet 6 to the reduction zone may be methane, ethane or othersaturated hydrocarbons that can form useful products such as ethylene,propylene and other unsaturated hydrocarbons with low carbon dioxideproduction.

The reduced oxygen transfer agents are conveyed via line 13 to theoxidation zone 5 of the system 3. An oxidizer, such as air, may beintroduced through inlet 8 into the oxidation zone 5 to cause oxidationand re-generation of the oxygen transfer agent. The exothermic heat ofoxidation resulting from the re-generation of the oxygen transfer agentmay then be transferred through the walls of a heat exchanger in theform of a coil 19 within the oxidation zone 5. A stream introduced intothe coil 19 through inlet 15 may include fluids that may result in theendothermic conversion of the contents of the stream. For example, thestream may comprise water resulting in the production of steam fromoutlet 17. Alternatively, the coil 19 may be a pyrolysis coil and thestream flowing through the coil 19 may comprise ethane resulting inethylene exiting the outlet 17. Any re-generated oxygen transfer agentsmay be conveyed back to the oxidation zone 4 via line 11.

The placement of the coils within the reaction zone is particularlybeneficial because of the effective heat transfer from the hot oxygentransfer agents through the walls of the coil. The exothermic heat ofre-oxidation of the oxygen transfer agents is used to provide the heatof reaction for converting, for example, water to steam or the pyrolysisof ethane to ethylene and other valuable products. In the case ofpyrolysis, systems according to the present invention may feed anyevolved hydrogen from the pyrolysis coil to the reduction zone of thesystem to reduce the oxygen transfer agent within the reduction zone.

By using a flameless combustion redox loop to supply heat to endothermicreactions in the systems and processes according to the presentinvention:

-   -   Carbon dioxide and NOx emissions may be essentially eliminated;        and    -   Very high heat transfer rates between the hot solid oxygen        transfer reagents through the coils in the oxidizing zone may        allow for shorter gas contact times within the coils. Therefore,        at the same conversion level of ethane, the amount of internal        wall coke formation will be less. This will extend the cycle        life of pyrolysis tubes, allowing for more time on stream and        less time when the pyrolysis tubes are not producing olefins        because carbon is being burned out of the tube.

Furthermore, when equation 16 is sufficiently exothermic, reactorconditions may be adjusted such that equation 2 occurs in parallel toequation 15 whereby hydrogen may also be produced from thedehydrogenation of hydrocarbons in the reactor. According to anotherembodiment of the present invention illustrated in FIG. 2B, twofixed-bed reactors 10, 12 are at least partially filled with a solidoxygen transfer agent 14, 16. A hydrocarbon feed line 18 for deliveringa hydrocarbon, such as ethane for example, includes a valve 22 toselectively direct the hydrocarbon feed to either the first reactor 10or the second reactor 12. If the first reactor 10 is selected, thehydrocarbon will pass through the layer of oxygen transfer agent 14,which promotes an ODH reaction, resulting in a product stream containingan unsaturated hydrocarbon, such as ethene, and water that exits thefirst effluent line 26. During this process in the first reactor 10, theoxygen transfer agent 14 is reduced over time. In order to regeneratethe agent, the feed stream is diverted through valve 22 to the secondfixed bed reactor 12, and an oxygen-containing gas stream, such as air,from feed line 20 is fed through valve 24 to the first reactor 10. Theoxygen-containing gas oxidizes the oxygen transfer agent 14, and theoxygen-depleted product gas exits effluent stream 28. The exothermicheat of oxidation of the oxygen transfer agent 14 may be utilized toheat a coil 34. A stream is selectively fed through the coil 34 via aninlet 30 having a corresponding valve. The stream may contain water, sothat the exothermic heat of oxidation of the oxygen transfer agent 14produces steam that exits the coil 34 via an outlet/valve 32.Alternatively, the coil 34 may by a pyrolysis coil, so that ethane maybe fed via inlet/valve 30 for pyrolytic conversion to ethylene.

As the oxygen transfer agent 14 in the first reactor 10 is beingregenerated through oxidation, the second reactor 12 is now producingthe unsaturated hydrocarbon that exits the effluent stream 26. Uponreaching the point where regeneration of the oxygen transfer agent 16 inthe second reactor 12 is necessary, the hydrocarbon feed and oxygencontaining gas feeds may be switched using the valves 22, 24. Similarlythe valves 30, 32 may also be switched to divert the stream to coil 36so that the exothermic heat of oxidation oxygen transfer agent 16 may beused for endothermic conversion of the contents of the stream. Thisarrangement provides a continuous production of unsaturated hydrocarbon,as well as continuous oxygen transfer agent regeneration. The systemsaccording to the present invention may be run in lean phase, dense phaseparticle transport, or include a free-falling bed, for example. Thereactors in the systems according to various embodiments of the presentinvention are not limited by the fluidization regime employed in eitherthe hydrocarbon oxidation or re-oxidation reactors.

By coupling exothermic oxidative dehydrogenation with endothermicpyrolysis, systems according to the present invention may:

-   -   Lower the overall exotherm of the ODH reaction and thereby make        temperature control of the reaction easier and less costly; and    -   Increase the selectivity of the desired dehydrated hydrocarbon        products and decrease unwanted oxidation products, such as        carbon dioxide and carbon monoxide.

The systems according to the present invention also have the ability toadjust the hydrogen to water product balance to better meet market needsor the effectiveness of downstream product separation equipment. Forexample, in the system 3 of FIG. 2A, the by-product water exiting outlet7 may be increased compared to hydrogen exiting outlet 17 by:

-   -   increasing the oxygen transfer agent circulation rate relative        to feed 6 to the reduction zone 4,    -   increasing the reaction rate in the reduction zone 4 compared to        the rate of pyrolysis in the coil 19,    -   circulating oxygen transfer agents with higher amounts of        transferable oxygen per weight of catalyst,    -   increasing the fluid density within the reduction zone, and    -   lowering the temperature in the oxidation zone 5 generated by        the heat of oxidation of the oxygen transfer agent.

Alternatively, the by-product water exiting outlet 7 may be decreasedcompared to hydrogen exiting outlet 17 by:

-   -   decreasing the oxygen transfer agent circulation rate relative        to the feed 6 to the reduction zone 4,    -   decreasing the reaction rate in reduction zone 4 compared to the        rate of pyrolysis in coil 19,    -   circulating oxygen transfer agents with lower amounts of        transferable oxygen per weight of catalyst,    -   increasing the heat capacity of the circulating oxygen transfer        agent,    -   decreasing the fluid density within the reduction zone, and    -   increasing the temperature in the oxidation zone 5 generated by        the heat of oxidation of the oxygen transfer agent.

The reaction pressure in the reactors should be optimized to produce thehighest yield of the desired oxidation products. Typical pressures ofoperation are between 0.1 and 20 atmospheres and more preferably between1 and 15 atmospheres. The preferred temperature for reaction in thereactor is 400° to 1,000° C. A more narrow operating range of 500-950°C. may be effective depending on the type and amount of promotersincluded with the oxygen transfer agent. In addition, it may bebeneficial to run the process at elevated pressures depending on thepromoter material. The temperature and pressure should also be selectedto allow for safe operation.

In yet another embodiment of the present invention, the above-describedsystems may further include the introduction of gas phase promoters intothe zones or vessels of the system that facilitate the desired reactionsof Equation (6). The addition of gas phase promoters may greatly enhancethe selectivity of the desired ODH products when used with oxygentransfer agents of the present invention. The gas phase promoters mayalso result in higher activity and extend the useful life of the oxygentransfer agents. Various gas phase promoters include, but are notlimited to, gas phase water, steam, CO₂, halide gases (such as chlorine,bromine, or fluorine), hydrogen halides (such as HCl, HBr, and HF), andsulfur containing gases such as hydrogen sulfide, oxides of sulfur, andorgano-sulfur compounds.

The oxygen transfer agents of the present invention may be used toconvert various forms of sulfur containing natural gas, which include,but are not limited to, biogas shale gas, associated gas from oil & gasproduction, coal gas, or any other form of methane containing gas thatalso contains some form of sulfur, either organic or inorganic sulfur,to higher hydrocarbons. The oxidation of H₂S contained in the naturalgas into SO₂ and SO₃ has been found to be synergistically beneficial forCO₂ sequestration, selectivity to C²⁺ products, and useful life of theoxygen transfer agent. Generally, all sulfur in the feed provided to areactor according to an embodiment of the present invention is convertedto SO₂, SO₃, or a mixture of the two sulfur gases.

Compared to current systems that utilize platinum-based materials toproduce unsaturated hydrocarbons, systems according to variousembodiments of the present invention advantageously generate low amountsof NOx. Systems that utilize platinum-based catalysts generally requirehigh temperature fuel combustion or de-coking to promote the generationof unsaturated hydrocarbons. High temperatures often lead to NOxproduction, unless the nitrogen is removed from the feed gases used tomaintain combustion in the furnaces. NOx production in theseplatinum-based systems may be avoided, but only by using expensive pureoxygen feed streams. The exotherm associated with the ODH reactionsperformed using oxygen transfer agents according to the presentinvention are relatively low compared to furnace temperatures andtherefore, generate little NOx. Thus, systems and methods according tothe present invention offer more environmentally friendly and lessexpensive alternatives to present day processes. The effluent producedby the reactor of the present invention may comprise unconvertedhydrocarbons as well as some lower value products, such as carbondioxide and carbon monoxide that may also be formed at lowconcentrations. Additional components of the effluent may includeoxygenated hydrocarbons, such as alcohols, which are formed inpreference to the production of carbon monoxide or carbon dioxide,resulting in an effluent from the reactor with a higher molarconcentration of oxygenated hydrocarbons than carbon monoxide or carbondioxide. It is within the scope of the present invention to recycle theeffluent. Similarly, lower value products, such as carbon oxides andwater, may be removed from the effluent prior to further treatment.

Preferably, further downstream processes include separation methods inorder to isolate polymer grade olefins. For example, ethylenefractionation may include one or more driers in order to remove waterprior to feeding the dried product to a distillation column. Thedistillation column preferably includes several stages to provide ahighly pure polymer grade ethylene product. The polymer grade olefinsmay then be sold as raw materials for the production of higher molecularweight products by oligomerization. Numerous catalysts and processes areknown for the oligomerization of olefins generally, and of ethyleneparticularly, all of which may be employed for converting the polymergrade olefins made according to the various methods of the presentinvention to higher molecular weight products. For example, phosphoricacid supported on a kieselguhr base has been widely used for makingpolymer gasoline (i.e., olefinic hydrocarbon liquids within the gasolineboiling range) from refinery gases. Other catalysts which have beenemployed for similar purposes include the oxides of cobalt, nickel,chromium, molybdenum and tungsten on supports such as alumina,silica-alumina, kieselguhr, carbon and the like. Higher hydrocarbonproducts of interest may include aviation fuels, kerosene, orintermediate refining streams.

Without intending to limit the scope of the claimed invention, mostoligomerization catalysts may be classified in one of two generalcategories: metal catalysts and acid catalysts. They may also beclassified as heterogeneous (solid) catalysts or homogeneous(liquid-phase) catalysts. Examples of metal catalysts that may be usedin a process according to the present invention for oligomerization ofunsaturated hydrocarbons, include nickel (note that these catalystsrequire a donor ligand and a Lewis acid), palladium, chromium, cobalt,titanium, tungsten, and rhenium. Examples of acid catalysts includephosphoric acid and acid catalysts based on alumina. Other acidcatalysts that may be used in the present invention are silaceous,crystalline molecular sieves. Such silica-containing crystallinematerials include materials which contain, in addition to silica,significant amounts of alumina, and generally known as “zeolites”, i.e.,crystalline aluminosilicates. Silica-containing crystalline materialsalso include essentially aluminum-free silicates. These crystallinematerials are exemplified by crystalline silica polymorphs (e.g.,silicalite and organosilicates), chromia silicates (e.g., CZM),ferrosilicates and galliosilicates, and borosilicates. Crystallinealuminosilicate zeolites are best exemplified by ZSM-5, ZSM-11, ZSM12,ZSM-21, ZSM-38, ZSM-23, and ZSM-35.

Metal oligomerization catalysts in general are more sensitive to feedimpurities, (e.g., water, carbon monoxide, dienes, etc.) than are theacid catalysts. Although homogeneous, metal catalysts are quite active,the need for dry feeds, solvents, and other measures to prevent catalystdeactivation and precipitation is disadvantageous and suggests anobvious advantage to supported, heterogeneous, metal catalyst.Homogeneous acid catalysts are effective but, are also corrosive andtend to form two liquid-phase systems with the non-polar hydrocarbonoligomerization products. Considering the foregoing observations,heterogeneous acid catalysts are the preferred catalyst for use in theoligomerization step of the process according to the present invention.Of the heterogeneous acid catalysts, acid zeolites are especiallypreferred, particularly zeolites of the ZSM-type and borosilicates.

While preferred embodiments of the invention have been shown anddescribed herein, it will be understood that such embodiments areprovided by way of example only. Numerous variations, changes, andsubstitutions will occur to those skilled in the art without departingfrom the spirit of the invention. Accordingly, it is intended that theappended claims cover all such variations as fall within the spirit andscope of the invention.

What is claimed is:
 1. A system for promoting endothermic conversionscomprising: a) a first portion defining a first inner volume at leastpartially filled with an oxygen transfer agent; b) a first supplycontaining one or more of hydrogen and a saturated hydrocarbon fluidlyconnected to a first inlet of the first inner volume; c) a first outletconveying one or more of carbon dioxide, water, and an unsaturatedhydrocarbon from the first inner volume; d) a second portion and a heatexchanger within the second portion, the second portion defining asecond inner volume at least partially filled with reduced oxygentransfer agent, the heat exchanger defining a third inner volumesegregated from the second inner volume; e) a second supply containingan oxidizing agent fluidly connected to a second inlet to the secondinner volume; and f) a third supply fluidly connected to the third innervolume, wherein the third supply contains a saturated hydrocarbon and,optionally, water; wherein the heat exchanger is configured to transferheat resulting from the oxidation of the reduced oxygen transfer agentin the second inner volume to the, third inner volume and the heat fromthe oxidation of the reduced oxygen transfer agent results inendothermic conversion of the saturated hydrocarbon in the third innervolume to an unsaturated hydrocarbon; and wherein at least one ofcondition i) or condition ii) is met: i) the first supply additionallycontains a sulfur containing gas; ii) the oxidizing agent is comprisedof at least one oxide of sulfur.
 2. The system of claim 1 furthercomprising a conveying means for transporting reduced oxygen transferagent from the first portion to the second portion and oxidized oxygentransfer agent from the second portion to the first portion providingthe heat of reaction for the endothermic conversion of the saturatedhydrocarbon.
 3. The system of claim 1, wherein the oxygen transfer agentcomprises at least one material capable of supplying oxygen andpromoting a reaction according to Equation (1) and the at least onematerial has a heat of reduction less than an exothermic heat ofoxidation, wherein Equation (1) iszC_(n)H_(2n+2−2β)+(z−1+δ)“O”→C_(z×n)+2−2β−2δ)+(z−1+δ) H₂O where z=thenumber of reacting molecules; n=the number of atomic units in thereacting molecule; β=the degree of unsaturation where the value is zerofor single bonds, one for double bonds and molecular rings, and two fortriple bonds; and δ=the change in the degree of unsaturation.
 4. Thesystem of claim 3, wherein the oxidation of the oxygen transfer agent isexothermic.
 5. The system of claim 3, wherein the oxygen transfer agentfurther comprises a second material having a thermal effusivity greaterthan 3,500 W·s^(0.5)/m²-K.
 6. The system of claim 3, wherein the oxygentransfer agent further comprises a second material having a thermaleffusivity greater than 10,000 W·s^(0.5)/m²-K.
 7. The system of claim 1,wherein the oxygen transfer agent comprises at least one material havinga thermal effusivity greater than 3,500 W·s^(0.5)/m²-K.
 8. The system ofclaim 1, wherein the oxygen transfer agent comprises at least onematerial having a thermal effusivity greater than 10,000 W·s^(0.5)/m²-K.9. The system of claim 1, wherein the one or more of carbon dioxide,water, and unsaturated hydrocarbon conveyed by the first outlet is theproduct of oxidative dehydrogenation of the saturated hydrocarbon of thefirst supply.
 10. The system of claim 1, wherein the heat from theoxidation of the reduced oxygen transfer agent results in endothermicconversion of the saturated hydrocarbon in the third inner volume to anunsaturated hydrocarbon.
 11. The system of claim 1, wherein theoxidizing agent comprises oxygen.
 12. The system of claim 1, wherein theheat exchanger is in the form of a pyrolysis coil.
 13. The system ofclaim 1, wherein the first supply containing the saturated hydrocarboncomprises a compound according to Formula (1)C_(n)H_(2n+2−2β)  (Formula (1)) where n=the number of atomic units inthe reacting molecule; β=the degree of unsaturation where the value iszero for single bonds, one for double bonds and molecular rings, and twofor triple bonds.
 14. A system for promoting endothermic conversionscomprising: a) a first portion defining a first inner volume at leastpartially filled with an oxygen transfer agent; b) a first supplycontaining one or more of hydrogen and a saturated hydrocarbon fluidlyconnected to a first inlet of the first inner volume; c) a first outletconveying one or more of carbon dioxide, water, and an unsaturatedhydrocarbon from the first inner volume; d) a second portion and a heatexchanger within the second portion, the second portion defining asecond inner volume at least partially filled with reduced oxygentransfer agent, the heat exchanger defining a third inner volumesegregated from the second inner volume; e) a second supply containingan oxidizing agent fluidly connected to a second inlet to the secondinner volume; f) a third supply fluidly connected to the third innervolume, wherein the third supply contains water; and wherein the heatexchanger is configured to remove heat resulting from the oxidation ofthe reduced oxygen transfer agent in the second inner volume; andwherein at least one of condition i) or condition ii) is met: i) thefirst supply additionally contains a sulfur containing gas; ii) theoxidizing agent is comprised of at least one oxide of sulfur.
 15. Thesystem of claim 14 further comprising a conveying means for transportingreduced oxygen transfer agent from the first portion to the secondportion and oxidized oxygen transfer agent from the second portion tothe first portion providing the heat of reaction for the endothermicconversion of the saturated hydrocarbon.
 16. The system of claim 14,wherein the oxygen transfer agent comprises at least one materialcapable of supplying oxygen and promoting a reaction according toEquation (1) and the at least one material has a heat of reduction lessthan an exothermic heat of oxidation, wherein Equation (1) iszC_(n)H_(2n+2−2β)+(z−1+δ)“O”→C_((z×n))H_(2(z×n)+2−2β−2δ)+(z−1+δ) H₂Owhere z=the number of reacting molecules; n=the number of atomic unitsin the reacting molecule; β=the degree of unsaturation where the valueis zero for single bonds, one for double bonds and molecular rings, andtwo for triple bonds; and δ=the change in the degree of unsaturation.17. The system of claim 16, wherein the oxidation of the oxygen transferagent is exothermic.
 18. The system of claim 16, wherein the oxygentransfer agent further comprises a second material having a thermaleffusivity greater than 3,500 W·s^(0.5)/m²-K.
 19. The system of claim16, wherein the oxygen transfer agent further comprises a secondmaterial having a thermal effusivity greater than 10,000 W·s^(0.5)/m²-K.20. The system of claim 14, wherein the oxygen transfer agent comprisesat least one material having a thermal effusivity greater than 3,500W·s^(0.5)/m²-K.
 21. The system of claim 14, wherein the oxygen transferagent comprises at least one material having a thermal effusivitygreater than 10,000 W·s^(0.5)/m²-K.
 22. The system of claim 14, whereinthe one or more of carbon dioxide, water, and unsaturated hydrocarbonconveyed by the first outlet is the product of oxidative dehydrogenationof the saturated hydrocarbon of the first supply.
 23. The system ofclaim 14, wherein the heat from, the oxidation of the reduced oxygentransfer agent results in endothermic conversion of the saturatedhydrocarbon in the third inner volume to an unsaturated hydrocarbon. 24.The system of claim 14, wherein the oxidizing agent comprises oxygen.25. The system of claim 14, wherein the heat exchanger is in the form ofa pyrolysis coil.
 26. The system of claim 14, wherein the first supplycontaining the saturated hydrocarbon comprises a compound according toFormula (1)C_(n)H_(2n+2−2β)  (Formula (1)) where n=the number of atomic units inthe reacting molecule; β=the degree of unsaturation where the value iszero for single bonds, one for double bonds and molecular rings, and twofor triple bonds.
 27. A system for promoting endothermic conversionscomprising: a) a first portion defining a first inner volume at leastpartially filled with an oxygen transfer agent; b) a first supplycontaining one or more of hydrogen and a saturated hydrocarbon fluidlyconnected to a first inlet of the first inner volume; c) a first outletconveying one or more of carbon dioxide, water, and an unsaturatedhydrocarbon from the first inner volume; d) a second portion, the secondportion defining a second inner volume at least partially filled withreduced oxygen transfer agent; and e) a second supply containing anoxidizing agent fluidly connected to a second inlet to the second innervolume; wherein at least one of condition i) or condition ii) is met:the first supply additionally contains a sulfur containing gas; ii) theoxidizing agent is comprised of at least one oxide of sulfur.
 28. Thesystem of claim 27 further comprising a conveying means for transportingreduced oxygen transfer agent from the first portion to the secondportion and oxidized oxygen transfer agent from the second portion tothe first portion providing the heat of reaction for the endothermicconversion of the saturated hydrocarbon.
 29. The system of claim 27,wherein the oxygen transfer agent comprises at least one materialcapable of supplying oxygen and promoting a reaction according toEquation (1) and the at least one material has a heat of reduction lessthan an exothermic heat of oxidation, wherein Equation (1) iszC_(n)H_(2n+2−2β)+(z−1+δ)“O”→C_((z×n))H_(2(z×n)+2−2β−2δ)+(z−1+δ) H₂Owhere z=the number of reacting molecules; n=the number of atomic unitsin the reacting molecule; β=the degree of unsaturation where the valueis zero for single bonds, one for double bonds and molecular rings, andtwo for triple bonds; and δ=the change in the degree of unsaturation.30. The system of claim 29, wherein the oxidation of the oxygen transferagent is exothermic.
 31. The system of claim 29, wherein the oxygentransfer agent further comprises a second material having a thermaleffusivity greater than 3,500 W·s^(0.5)/m²-K.
 32. The system of claim29, wherein the oxygen transfer agent further comprises a secondmaterial having a thermal effusivity greater than 10,000 W·s^(0.5)/m²-K.33. The system of claim 27, wherein the oxygen transfer agent comprisesat least one material having a thermal effusivity greater than 3,500W·s^(0.5)/m²-K. The system of claim 27, wherein the oxygen transferagent comprises at least one material having a thermal effusivitygreater than 10,000 W·s^(0.5)/m²-K.
 35. The system of claim 27, whereinthe one or more of carbon dioxide, water, and unsaturated hydrocarbonconveyed by the first outlet is the product of oxidative dehydrogenationof the saturated hydrocarbon of the first supply.
 36. The system ofclaim 27, wherein the oxidizing agent comprises oxygen.
 37. The systemof claim 27, wherein the first supply containing the saturatedhydrocarbon comprises a compound according to Formula (1)C_(n)H_(2n+2−2β)  (Formula (1)) where n=the number of atomic units inthe reacting molecule; β=the degree of unsaturation where the value iszero for single bonds, one for double bonds and molecular rings, and twofor triple bonds.